The present invention relates to a process for preparing polymers based on monomers having a C.dbd.C double bond by homopolymerization or copolymerization of these monomers in the presence of a catalyst system comprising a metallocene complex A) and a compound B) capable of forming metallocenium ions and, if desired, an organometallic compound of main group I, II or III of the Periodic Table of the Elements C), catalyst systems which are suitable for polymerizing monomers having a C.dbd.C double bond and comprise as active constituents
A) a metallocene complex of the formula (I) ##STR2##
where the substituents and indices have the following meanings:
R.sup.1 to R.sup.11 are hydrogen, C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear C.sub.1 -C.sub.6 -alkyl groups as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals R.sup.1 to R.sup.8 may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R.sup.12).sub.3, PA0 M is a metal of transition groups III to VI of the 40 Periodic Table of the Elements or a metal of the lanthanide series, PA0 X are identical or different and are hydrogen, halogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, C.sub.1 -C.sub.10 -alkoxy or C.sub.6 -C.sub.15 -aryloxy PA0 n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1, PA0 R.sup.1 to R.sup.11 are hydrogen, C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear C.sub.1 -C.sub.6 -alkyl groups as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals R.sup.1 to R.sup.8 may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R.sup.12).sub.3, PA0 M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series, PA0 X are identical or different and are hydrogen, halogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, C.sub.1 -C.sub.10 -alkoxy or C.sub.6 -C.sub.15 -aryloxy PA0 n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1. PA0 R.sup.1 to R.sup.11 are hydrogen, C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear C.sub.1 -C.sub.6 -alkyl groups as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals R.sup.1 to R.sup.8 may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R.sup.12).sub.3, PA0 M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series PA0 X are identical or different and are hydrogen, halogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, C.sub.1 -C.sub.10 -alkoxy or C.sub.6 -C.sub.15 -aryloxy PA0 n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1, PA0 R.sup.1 to R.sup.11 are hydrogen, C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear C.sub.1 -C.sub.6 -alkyl groups as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals R.sup.1 to R.sup.8 may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R.sup.2).sub.3, PA0 M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series, PA0 X are identical or different and are hydrogen, halogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, C.sub.1 -C.sub.10 -alkoxy or C.sub.6 -C.sub.15 -aryloxy PA0 n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1, PA0 R.sup.1 to R.sup.11 are hydrogen, C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear C.sub.1 -C.sub.6 -alkyl groups as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals R.sup.1 to R.sup.8 may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R.sup.12).sub.3, PA0 M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series, PA0 X are identical or different and are hydrogen, halogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, C.sub.1 -C.sub.10 -alkoxy or C.sub.6 -C.sub.15 -aryloxy PA0 n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1, PA0 R.sup.13 is hydrogen or C.sub.1 -C.sub.4 -alkyl, PA0 R.sup.14 to R.sup.18 are, independently of one another, hydrogen, C.sub.1 -C.sub.12 -alkyl, C.sub.6 -C.sub.18 -aryl, halogen or two adjacent radicals together form a cyclic group having from 4 to 15 carbon atoms. PA0 R.sup.13 is hydrogen PA0 R.sup.14 to R.sup.1 are hydrogen, C.sub.1 -C.sub.4 -alkyl, chlorine or phenyl or two adjacent radicals together form a cyclic group having from 4 to 12 carbon atoms, resulting in compounds of the formula II which are, for example, naphthalene derivatives or anthracene derivatives. PA0 styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene, 1,4-divinylbenzene, 4-vinylbiphenyl, 2-vinylnaphthalene and 9-vinylanthracene. PA0 R.sup.1 to R.sup.11 are hydrogen, C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear C.sub.1 -C.sub.6 -alkyl groups as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals R.sup.1 to R.sup.8 may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R.sup.12).sub.3, PA0 M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series, PA0 X are identical or different and are hydrogen, halogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, C.sub.1 -C.sub.10 -alkoxy or C.sub.6 -C.sub.15 -aryloxy PA0 n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1. PA0 M is a metal of transition group IV of the Periodic Table of the Elements, in particular titanium, PA0 X is C.sub.1 -C.sub.10 -alkyl, C.sub.1 -C.sub.10 -alkoxy or halogen and PA0 n is 3. PA0 where R.sup.19 is a C.sub.1 -C.sub.4 -alkyl group, preferably a methyl or ethyl group, and k is an integer from 5 to 30, preferably from 10 to 25. PA0 M.sup.1 is an element of main group III of the Periodic Table, in particular B, Al or Ga, preferably B, PA0 X.sup.1,X.sup.2 and X.sup.3 are hydrogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine, in particular haloaryls, preferably pentafluorophenyl. PA0 Y is an element of main groups I to VI or of transition groups I to VIII of the Periodic Table, PA0 Q.sub.1 to Q.sub.z are singly negatively charged radicals such as C.sub.1 -C.sub.28 -alkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 carbon atoms in the aryl radical and from 1 to 28 carbon atoms in the alkyl radical, C.sub.1 -C.sub.10 -cycloalkyl which may bear C.sub.1 -C.sub.10 -alkyl groups as substituents, halogen, C.sub.1 -C.sub.28 -alkoxy, C.sub.6 -C.sub.15 -aryloxy, silyl or mercaptyl groups, PA0 a is an integer from 1 to 6, PA0 z is an integer from 0 to 5 and PA0 d corresponds to the difference a - z, but d is greater than or equal to 1. PA0 R.sup.20 to R.sup.22 are hydrogen, fluorine, chlorine, bromine, iodine or C.sub.1 -C.sub.12 -alkyl, preferably C.sub.1 --C.sub.8 -alkyl.
where R.sup.12 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or C.sub.3 -C.sub.10 -cycloalkyl,
and
B) a compound capable of forming metallocenium ions and, if desired, C) an organometallic compound of main group I, II or III of the Periodic Table of the Elements, metallocene complexes of the formula (I) ##STR3##
where the substituents and indices have the following meanings:
where R.sup.12 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or C.sub.3 -C.sub.10 -cycloalkyl,
and
The present invention further relates to polymers which are based on monomers having a C.dbd.C double bond and are obtainable by homopolymerization or copolymerization of these monomers in the presence of a catalyst system comprising a metallocene complex A) and a compound B) capable of forming metallocenium ions and, if desired, an organometallic compound of main group I, II or III of the Periodic Table of the Elements C), and also fibers, films and moldings comprising these polymers and the use of metallocene complexes (I) as components in catalyst systems or as catalysts.
Syndiotactic polymers of styrene are known. Owing to their property profile, eg. high hardness, high stiffness, dimensional stability and low dielectric constants, they can be used, for example, as electrical or mechanical components.